WO2014178332A1

WO2014178332A1 - Gas barrier film and method for producing same

Info

Publication number: WO2014178332A1
Application number: PCT/JP2014/061624
Authority: WO
Inventors: 西尾　昌二
Original assignee: コニカミノルタ株式会社
Priority date: 2013-05-01
Filing date: 2014-04-24
Publication date: 2014-11-06
Also published as: JPWO2014178332A1; US20160059261A1

Abstract

The purpose of the present invention is to provide a gas barrier film which is obtained by forming a second barrier layer from a coating liquid containing a polysilazane on a vapor deposition film, and which exhibits excellent adhesion of the barrier layer and is free from a composition change even if exposed to high temperature and high humidity, thereby maintaining high barrier properties. A gas barrier film according to the present invention is characterized by comprising a first barrier layer (a first inorganic layer) that is formed on at least one surface of a base (a supporting body) by a vapor deposition method, and a second barrier layer (a second inorganic layer) that is formed on the first inorganic layer by modifying a polysilazane coating film. This gas barrier film is also characterized in that the polysilazane coating film contains nanoparticles of a metal oxide and/or a metal nitride and the modification of the polysilazane coating film is carried out by irradiating the polysilazane coating film with vacuum ultraviolet light having a wavelength of 200 nm or less.

Description

Gas barrier film and method for producing the same

The present invention relates to a gas barrier film and a method for producing the same. More specifically, the present invention relates to a gas barrier film having excellent barrier layer adhesion and low water vapor and oxygen permeability, and further, an electronic device using the gas barrier film, particularly an organic EL element (organic electroluminescent element). ) And the like.

Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on a plastic substrate or film surface is used for packaging an article that requires blocking of various gases such as water vapor and oxygen, Widely used in packaging applications to prevent the deterioration of food, industrial products and pharmaceuticals. In addition to packaging applications, there are demands for the development of flexible electronic devices such as flexible solar cell elements, liquid crystal display elements, organic electroluminescence (hereinafter abbreviated as organic EL) elements, and many studies have been made. ing. However, in these flexible electronic devices, since a gas barrier property at a glass substrate level is required, gas barrier films having sufficient performance have not been obtained at present.

As a method for forming such a gas barrier film, a chemical deposition method (plasma CVD method) in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used and grown on a substrate while oxygen plasma oxidation is performed under reduced pressure. : Chemical Vapor Deposition) and vapor deposition methods such as physical deposition methods in which metal silicon is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen are known.

These inorganic vapor deposition methods have been preferably applied to the formation of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride, and the composition of inorganic films for obtaining good gas barrier properties, and Many studies have been made on the layer structure including these inorganic films.

However, it is very difficult to form a film having no defects by the vapor phase method as described above. For example, it is necessary to extremely reduce the film forming rate to suppress the generation of defects. For this reason, the gas barrier property required for flexible electronic devices has not been obtained at an industrial level where productivity is required. Studies such as simply increasing the film thickness of the inorganic film by the vapor phase method or laminating a plurality of inorganic films have been made, but since defects grow continuously or cracks increase, the gas barrier property is improved. Has not reached.

Such defects in the inorganic film, for example, in the case of organic EL, cause the generation of black spots called dark spots that do not emit light, and the size of the dark spots grows under high temperature and high humidity, which also affects the durability of the element itself. Will be given.

On the other hand, in the past, the present inventor applied a solution of an inorganic precursor compound on the above-mentioned gas-phase-forming film and dried it as one of barrier layer forming methods in addition to such gas-layer film formation. By modifying the applied layer with heat or light, the defect part of the inorganic film formed by the above-mentioned vapor phase method can be effectively repaired, and further, the gas barrier property of the laminated film itself can be improved. I went. In particular, studies have been made to develop a high gas barrier property by repairing the above-described defective portion by using polysilazane as an inorganic precursor compound (Japanese Patent Laid-Open No. 2012-106421).

Polysilazane (for example, perhydroxypolysilazane) is a compound having — (SiH ₂ —NH) — as a basic skeleton. When polysilazane is subjected to heat treatment or wet heat treatment in an oxidizing atmosphere, it changes into silicon oxide via silicon oxynitride. At this time, since a direct substitution reaction from nitrogen to oxygen is caused by oxygen or water vapor in the atmosphere, it changes to silicon oxide with a relatively small volume shrinkage, so there are relatively few defects in the film due to the volume shrinkage. It is known that a dense film can be obtained. By controlling the oxidizing property of the atmosphere, a relatively dense silicon oxynitride film can be obtained.

However, a high temperature is required to form a dense silicon oxynitride film or silicon oxide film by thermal modification or wet heat modification of polysilazane, and it has been difficult to apply to a flexible substrate such as plastic.

As a means for solving such a problem, a method of forming a silicon oxynitride film or a silicon oxide film by applying vacuum ultraviolet light to a coating film formed from a polysilazane solution has been proposed.

Bonding of atoms is called a photon process using light energy having a wavelength of 100 to 200 nm called vacuum ultraviolet light (hereinafter also referred to as “VUV” or “VUV light”) having an energy larger than the bonding force between each atom of polysilazane. A silicon oxynitride film or a silicon oxide film can be formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by the action of only photons. In addition, this method is also suitable for manufacturing in a roll-to-roll system with good productivity.

Specifically, usually, when polysilazane is applied onto a resin film substrate and similarly irradiated with ultraviolet rays, the vicinity of the surface of the irradiated surface is modified to form a barrier layer (high nitrogen concentration layer). At the same time, an oxidation behavior presumed to be caused by moisture from the substrate side occurs, and a behavior has been reported in which the inside of the barrier layer becomes an oxide film (silicon oxide layer) (for example, International Publication No. 2011/007543).

As a result of intensive studies, the inventors of the present invention formed a coating liquid containing a polysilazane solution on the first barrier layer formed by the above-described vapor phase method, modified the polysilazane by ultraviolet irradiation, and then applied the second. In the gas barrier film in which the barrier layer is formed, a new problem has been found that when the film is exposed to a high-temperature and high-humidity environment, the formed barrier layer disappears and the barrier property is remarkably lowered.

Especially when the barrier layer is in the lower layer, the surface of the polysilazane film modified by UV irradiation is oxidized due to the effect of oxygen and moisture taken in from the outside, but the oxygen element is not taken into the inside sufficiently, and the reaction However, it has been found that there is an unmodified region that is insufficient, and that the unmodified region is exposed to high temperature and high humidity as described above, which causes deterioration of the barrier layer.

Therefore, the present invention has been made in view of the above circumstances, and the object thereof is to form a second barrier layer formed from a coating liquid containing polysilazane on a vapor deposition film, and to have excellent adhesion of the barrier layer. An object of the present invention is to provide a barrier film capable of preventing composition changes even when exposed to a high temperature and high humidity environment and maintaining high barrier properties.

The present inventor conducted intensive research to solve the above problems. As a result, in the gas barrier film having a vapor deposition film and a polysilazane modified film, by introducing at least one kind of metal oxide nanoparticles and metal nitride nanoparticles into the polysilazane modified film, The inventors have found that this can be solved, and have completed the present invention.

That is, the present invention modifies the first barrier layer (first inorganic layer) formed by vapor deposition on at least one surface of the substrate (support) and the polysilazane coating film on the first inorganic layer. A gas barrier film comprising a second barrier layer (second inorganic layer) formed by the method, wherein the polysilazane coating film contains at least one kind of nanoparticles of metal oxide and metal nitride The polysilazane coating film is modified by irradiating the polysilazane coating film with vacuum ultraviolet light having a wavelength of 200 nm or less.

It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the 1st inorganic layer which concerns on this invention. It is a schematic diagram which shows an example of the other manufacturing apparatus used for formation of the 1st inorganic layer which concerns on this invention. It is a bead mill for controlling the particle size of the nanoparticles according to the present invention.

The present invention includes a first barrier layer (first inorganic layer) formed by vapor deposition on at least one surface of a substrate (support), and a polysilazane coating film on the first inorganic layer. A gas barrier film comprising a second barrier layer (second inorganic layer) formed, wherein the polysilazane coating film contains at least one kind of nanoparticles of a metal oxide and a metal nitride, The polysilazane coating film is modified by irradiating the polysilazane coating film with vacuum ultraviolet light having a wavelength of 200 nm or less. According to the above configuration, since the soft unmodified region of polysilazane is reinforced by the hard nanoparticles, a gas barrier film having a high barrier property under high temperature and high humidity is provided.

When the barrier layer is formed by modifying the polysilazane film by irradiation with vacuum ultraviolet light, the barrier layer is modified from the surface side irradiated with vacuum ultraviolet light. For this reason, oxygen and moisture hardly diffuse inside the barrier layer, and an unreacted (unmodified) region where ammonia can be generated by hydrolysis remains. This unreacted (unmodified) region reacts gradually under high temperature and high humidity to produce a by-product, and the diffusion of the by-product may cause the barrier layer to be deformed or destroyed. As a result, there is a problem that the barrier property is gradually lowered.

In order to obtain higher gas barrier properties, it is necessary to increase the amount of ultraviolet light that modifies the polysilazane film and to stack a plurality of barrier layers. However, as the degree of progress of modification and the number of layers increase and the film becomes thicker, the productivity decreases and the internal shrinkage stress in the film increases, and the flexibility (flexibility) that is a characteristic of a flexible gas barrier film ) And the durability against physical stress such as bending is also reduced.

On the other hand, the gas barrier film of the present invention is excellent in adhesion of the barrier layer and has low water vapor and oxygen permeability even under high temperature and high humidity.

The gas barrier film of the present invention has excellent barrier layer adhesion and low water vapor and oxygen permeability even under high temperature and high humidity. The detailed reason is unknown, but it is considered as follows. It is done.

In an inorganic layer formed by modifying a conventional polysilazane coating film that does not contain nanoparticles, many unmodified portions containing a large amount of nitrogen remain. The reason why the polysilazane layer containing many unmodified parts deteriorates immediately in the wet heat environment is considered to be due to the weak physical and chemical strength.

At least one kind of metal oxide and metal nitride contained in the polysilazane-containing coating solution according to the present invention has a functional group such as a hydroxyl group on the surface, which is a polysilazane Si—N bond. By reacting, the nanoparticle surface is modified with polysilazane. The second inorganic layer of the present invention obtained by modifying the polysilazane coating film formed by applying and drying such a polysilazane-containing coating solution is in a state where the soft unmodified region is reinforced with hard nanoparticles. It is considered that high strength can be obtained even in an environment. Also, when carbon or nitrogen is contained in the lower vapor deposition film (first inorganic layer), the first inorganic layer becomes more flexible and the surface reactivity is improved, and the interaction with the second inorganic layer becomes stronger. Conceivable. The inorganic layer obtained in this way is in a state in which a large amount of nitrogen is left, so that it is considered that both high gas barrier properties and wet heat resistance can be achieved.

Note that the above mechanism is based on estimation, and the present invention is not limited to the above mechanism.

Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment.

In this specification, unless otherwise specified, “X to Y” indicating a range means “X or more and Y or less”, and measurement of operation and physical properties is room temperature (20 to 25 ° C.) / Relative humidity 40 to 50. Measured under the condition of%.

《Gas barrier film》
The gas barrier film of the present invention has a substrate and a barrier layer. The gas barrier film of the present invention may further contain other members. The gas barrier film of the present invention can be applied, for example, between the base material and the barrier layer, between the barrier layer and the barrier layer, on the barrier layer, or on the surface where the barrier layer of the base material is not formed. You may have the member. Here, the other members are not particularly limited, and members used for conventional gas barrier films can be used in the same manner or appropriately modified. Specifically, functional layers such as a smooth layer, an anchor coat layer, a bleed-out prevention layer, a protective layer, a hygroscopic layer, and an antistatic layer can be used.

In the present invention, the first barrier layer and the second barrier layer may exist one by one or may have a laminated structure of two or more layers. In addition, the first barrier layer and the second barrier layer may be alternately stacked, and the first barrier layers or the second barrier layers may be adjacent to each other.

Furthermore, in the present invention, the barrier layer may be formed on at least one surface of the substrate. For this reason, the gas barrier film of the present invention includes both a form in which a barrier layer is formed on one surface of a substrate and a form in which barrier layers are formed on both surfaces of a substrate.

[Base material]
The substrate used in the present invention is not particularly limited as long as it is a long support and can hold the barrier layer.

As the substrate, a plastic film or sheet is usually used, and a film or sheet made of a colorless and transparent resin is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, a hard coat layer, and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

These base materials may be used alone or in combination of two or more.

The thickness of the base material used in the gas barrier film according to the present invention is not particularly limited because it is appropriately selected depending on the application, but is typically preferably 5 to 500 μm, more preferably 25 to 250 μm. .

[Smooth layer (underlayer, primer layer)]
The gas barrier film of the present invention may have a smooth layer (underlying layer, primer layer) between the surface of the substrate having the barrier layer, preferably between the substrate and the barrier layer. The smooth layer is provided in order to flatten the rough surface of the substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer with the protrusions on the substrate and to flatten the surface. Such a smooth layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, the gas barrier film of the present invention preferably further has a smooth layer containing a carbon-containing polymer between the substrate and the barrier layer.

The smooth layer may also contain a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.

Examples of the active energy ray-curable material used for forming the smooth layer include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, and polyester. Examples include compositions containing polyfunctional acrylate monomers such as acrylates, polyether acrylates, polyethylene glycol acrylates, and glycerol methacrylates. Specifically, UV curable organic / inorganic hybrid hard coating material manufactured by JSR Corporation
An OPSTAR (registered trademark) series (a compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) can be used. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.

The method for forming the smooth layer is not particularly limited, but a coating solution containing a curable material is applied to a dry coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method, or a vapor deposition method. After applying the coating method to form a coating film, irradiation with active energy rays such as visible light, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron beams, and / or heating, the coating films are formed. A method of forming by curing is preferred.

The smoothness of the smooth layer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less.

The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (atomic force microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens of times with a stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

The thickness of the smooth layer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

[Anchor coat layer]
On the surface of the substrate according to the present invention, an anchor coat layer may be formed as an easy-adhesion layer for the purpose of improving adhesion (adhesion). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., “X-12-2400” 3% isopropyl alcohol solution) can be used.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

[Bleed-out prevention layer]
In the base material having a smooth layer, unreacted oligomers or the like may migrate from the base material to the surface during heating, and the base material surface may be contaminated. The bleed-out prevention layer has a function of suppressing contamination of the substrate surface. When it has a bleed-out prevention layer, a bleed-out prevention layer is normally provided in the surface opposite to the smooth layer of the base material which has a smooth layer.

The bleed-out prevention layer may have the same configuration as the smooth layer as long as it has the above function. That is, the bleed-out prevention layer can be formed by applying a photosensitive resin composition on a substrate and then curing it.

When at least one control layer selected from the group consisting of the above-described anchor coat layer, smooth layer, and bleed-out layer is formed on the base material, the total thickness of the base material and the control layer is 5 It is preferably ˜500 μm, more preferably 25 to 250 μm.

Further, an intermediate layer may be formed between the first inorganic layer and the second inorganic layer.

The intermediate layer can be formed for the purpose of enhancing the gas barrier property of the first barrier layer, for the purpose of enhancing the adhesion between the first barrier layer and the second barrier layer, or the like. Under the present circumstances, the said intermediate | middle layer is formed in the range which does not impair the effect of this invention.

The intermediate layer may be any of an inorganic layer, an organic layer, an organic-inorganic hybrid layer, and the like, but is preferably an inorganic layer.

The material for the inorganic layer is not particularly limited, and may be the same material as the first inorganic layer or the second inorganic layer, or a different material may be used. Examples of the material used for the inorganic layer of the intermediate layer include zirconia and titania.

As a material for the organic layer, a polymer material obtained by polymerizing a crosslinkable monomer can be used. The crosslinkable monomer is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, and an oxirane group.

Silsesquioxane can be used as the material of the organic / inorganic hybrid layer.

The thickness of the intermediate layer is preferably 0.05 to 10 nm, and more preferably 0.1 to 5 nm. However, when the same material as the first inorganic layer or the second inorganic layer is used as the material of the intermediate layer, and the thickness of the intermediate layer exceeds 10 nm, it belongs to the first inorganic layer or the second inorganic layer. .

[First barrier layer (first inorganic layer)]
The first inorganic layer is formed by vapor deposition, but can be formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD). Here, the first inorganic layer may include at least one oxide, nitride, oxynitride, or oxycarbide selected from the group consisting of silicon, aluminum, and titanium. As the at least one oxide, nitride, oxynitride, oxycarbide or oxynitride carbide selected from the group consisting of silicon, aluminum, and titanium, specifically, silicon oxide (SiO ₂ ), silicon nitride, These composites include silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon carbide, aluminum oxide, titanium oxide, and aluminum silicate. Of these, silicon oxynitride (SiON), silicon nitride (SiN), hydrogenated silicon nitride (SiNH), silicon oxycarbide (SiOC), silicon oxide (SiO ₂ ), aluminum silicate (SiAlO) and silicon oxynitride carbide (SiONC). These may contain other elements as secondary components.

A 1st inorganic layer has gas barrier property by having the above compounds. Here, when the gas barrier property of the first inorganic layer is calculated using a laminate in which the first inorganic layer is formed on the base material, the permeated water amount measured by the method described in Examples below is 0. is preferably 1g ^/ (m 2 · 24h) or less, and more preferably 0.01g ^/ (m 2 · 24h) or less.

The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. For example, a sputtering method (DC sputtering, RF Sputtering, ion beam sputtering, magnetron sputtering, etc.), vacuum deposition, ion plating, and the like.

As a raw material compound, a silicon compound, a titanium compound, and an aluminum compound are used. Conventionally known compounds can be used for these.

In addition, the decomposition gas used when decomposing the raw material gas containing metal to obtain the inorganic compound includes hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide. Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, and water vapor. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

The thickness of the first inorganic layer of the present invention is preferably 10 to 1000 nm, and more preferably 150 to 200 nm. If it is said range, it will be hard to be influenced by a defect part and the part with the low density between crystals, and high gas barrier property will be acquired. Further, even when it is deformed, the destruction of the inorganic layer can be reduced, which is preferable in practice.

Hereinafter, the plasma CVD method which is a preferable form among the CVD methods will be described in detail.

FIG. 1 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming the first inorganic layer according to the present invention.

In FIG. 1, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface side inside the vacuum chamber 102. Further, a cathode electrode 103 is disposed on the ceiling side inside the vacuum chamber 102 at a position facing the susceptor 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are disposed outside the vacuum chamber 102. A heat medium is disposed in the heat medium circulation system 106. The heat medium circulation system 106 stores a pump for moving the heat medium, a heating device for heating the heat medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heat medium, and a set temperature of the heat medium. A heating / cooling device 160 having a storage device is provided. For the details of the vacuum plasma CVD apparatus shown in FIG. 1, International Publication No. WO12 / 014653 can be referred to.

(Other suitable forms of the first inorganic layer)
As another preferred embodiment of the first inorganic layer of the present invention, the first inorganic layer includes a first inorganic layer containing carbon, silicon, and oxygen as constituent elements. A more preferred form is the first inorganic layer that satisfies the following requirements (i) to (ii).

(I) The distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atomic ratio) A distribution curve showing the relationship between L and the oxygen distribution curve showing the relationship between the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen); In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values,
(Ii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more.

Having such a composition is preferable from the viewpoint of achieving both high gas barrier properties and flexibility.

Furthermore, in the region of 90% or more of the total thickness of the first inorganic layer, the average atomic ratio of each atom to the total amount (100 at%) of silicon atoms, oxygen atoms and carbon atoms is expressed by the following formula (A) or (B It is preferable to have an order of magnitude relationship represented by

Formula (A)
(Carbon average atomic ratio) <(silicon average atomic ratio) <(oxygen average atomic ratio)
Formula (B)
(Oxygen average atomic ratio) <(silicon average atomic ratio) <(carbon average atomic ratio)
If so, the bending resistance is further improved, which is more preferable.

Hereinafter, the preferred embodiment will be described.

(I) The distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atoms Ratio), a silicon distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of oxygen), and In the carbon distribution curve showing the relationship between L and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values. preferable. The first inorganic layer preferably has at least three extreme values in the carbon distribution curve, more preferably at least four extreme values, but may have five or more extreme values. When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the film thickness of the barrier layer, it cannot be specified unconditionally.

Here, in the case of having at least three extreme values, one extreme value of the carbon distribution curve and the first inorganic layer in the film thickness direction of the first inorganic layer at the extreme value adjacent to the extreme value. The absolute value of the difference in distance (L) from the surface (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm or less. It is particularly preferred. With such a distance between extreme values, the first inorganic layer has moderate flexibility because the first inorganic layer has sites with a high carbon atom ratio (maximum value) at an appropriate period. In addition, the generation of cracks when the gas barrier film is bent can be more effectively suppressed / prevented. In this specification, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer. Further, in this specification, the maximum value is a point where the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from increase to decrease when the distance from the surface of the first inorganic layer is changed, And the atom of the element at a position where the distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer from the point is further changed within the range of 4 to 20 nm, rather than the value of the atomic ratio of the element at that point This is the point at which the ratio value decreases by 3 at% or more. That is, it is sufficient that the atomic ratio value of the element is reduced by 3 at% or more in any range when changing in the range of 4 to 20 nm. This varies depending on the film thickness of the first inorganic layer. For example, when the film thickness of the first inorganic layer is 300 nm, the atomic ratio value of the element at the position where the distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer is changed by 20 nm is 3 at. % Is preferable. Furthermore, the minimum value in the present specification is a point where the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from decrease to increase when the distance from the surface of the first inorganic layer is changed, and The atomic ratio of the element at the position where the distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer is further changed within the range of 4 to 20 nm from the value of the atomic ratio of the element at that point This means that the value increases by 3 at% or more. That is, when changing in the range of 4 to 20 nm, the atomic ratio value of the element only needs to increase by 3 at% or more in any range. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is particularly high because the smaller the distance between the extreme values, the higher the effect of suppressing / preventing crack generation when the gas barrier film is bent. Not limited.

Further, in the first inorganic layer, (ii) the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. Preferably, it is 7 at% or more. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more, the gas barrier performance during bending is enhanced. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values.

Also, in the region of 90% or more (upper limit: 100%) of the film thickness of the first inorganic layer, (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in order (atomic ratio) Is preferably O> Si> C). By satisfying such conditions, the resulting gas barrier film has sufficient gas barrier properties and flexibility. Here, in the carbon distribution curve, the relationship of the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the thickness of the barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). Here, “at least 90% or more of the thickness of the barrier layer” does not need to be continuous in the barrier layer, and only needs to satisfy the above-described relationship at a portion of 90% or more.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time is the distance (L) from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer in the film thickness direction. Since there is a general correlation, the “distance from the surface of the first inorganic layer in the film thickness direction of the first inorganic layer” is calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface of one inorganic layer can be employed. In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve were prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ );
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
X-ray photoelectron spectrometer: manufactured by Thermo Fisher Scientific, model name “VG Theta Probe”;
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

From the viewpoint of forming a first inorganic layer that is uniform over the entire film surface and has excellent gas barrier properties, the first inorganic layer is substantially uniform in the film surface direction (direction parallel to the surface of the first inorganic layer). It is preferable that Here, the fact that the first inorganic layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at any two measurement points on the film surface of the first inorganic layer by XPS depth profile measurement. When the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Furthermore, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first inorganic layer in the film thickness direction of at least one of the first inorganic layers to be formed, and the atomic ratio of carbon (C, unit: at%) In the relationship, the condition expressed by the following formula (1) is satisfied.

When the first inorganic layer has a sublayer, a plurality of sublayers that satisfy all of the above conditions (i) to (ii) may be stacked to form the first inorganic layer. When two or more sublayers are provided, the materials of the plurality of sublayers may be the same or different.

The layer satisfying the requirements of (i) to (ii), which is a preferred form of the first inorganic layer, is preferably a layer formed by a plasma CVD (PECVD) method, and a substrate is formed as a pair of films. More preferably, it is formed on a roller and formed by a plasma CVD method in which plasma is generated by discharging between the pair of film forming rollers. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

When generating plasma in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers has the above-mentioned base. More preferably, a material is disposed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. Compared with the plasma CVD method using no roller, the film formation rate can be doubled, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled, and it is efficient. It is possible to form a layer that satisfies all of the above conditions (i) to (ii).

Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the barrier layer is preferably a layer formed by a continuous film forming process.

Also, from the viewpoint of productivity, it is preferable to form the first inorganic layer on the surface of the substrate by a roll-to-roll method. Further, an apparatus that can be used when producing the first inorganic layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of pairs. It is preferable that the apparatus has a configuration capable of discharging between the film forming rollers. For example, when the manufacturing apparatus shown in FIG. 2 is used, a roll-to-roll system is used while using a plasma CVD method. It can also be manufactured.

Hereinafter, the method for forming the first inorganic layer will be described in more detail with reference to FIG. FIG. 2 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first inorganic layer. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32,

transport rollers

33, 34, 35, and 36,

film formation rollers

39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And

magnetic field generators

43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the

film forming rollers

39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic

field generating apparatuses

43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump. Details relating to the apparatus can be referred to conventionally known documents, for example, Japanese Patent Application Laid-Open No. 2011-73430.

As described above, as a more preferable aspect of the present embodiment, the first inorganic layer is formed by a plasma CVD method using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode shown in FIG. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently produce the first inorganic layer having both the barrier performance and the barrier performance. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

[Second barrier layer (second inorganic layer)]
The second barrier layer is formed by applying a coating liquid containing a polysilazane compound and nanoparticles (hereinafter also referred to as “nanoparticle-containing polysilazane-containing coating liquid”) onto a substrate, and applying a vacuum having a wavelength of 200 nm or less to the obtained coating film. It is formed by irradiating with ultraviolet light (step (1)).

(Nanoparticle-containing polysilazane-containing coating solution)
The nanoparticle-containing polysilazane-containing coating solution contains a polysilazane compound and nanoparticles.

Polysilazane compound A polysilazane compound is a polymer having a bond such as Si—N, Si—H, or N—H in its structure, such as SiO ₂ , Si ₃ N ₄ , and their intermediate solid solution SiO _x N _y . Functions as an inorganic precursor.

The polysilazane compound is not particularly limited, but is preferably a compound that is converted to silica by being converted to silica at a relatively low temperature in consideration of the modification treatment described later, for example, in JP-A-8-112879. It is preferable that it is a compound which has the main skeleton which consists of a unit represented by the following general formula (1) of description.

In the general formula (1), R ¹ , R ² and R ³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. At this time, R ¹ , R ² and R ³ may be the same or different. Here, examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the aryl group include aryl groups having 6 to 30 carbon atoms. More specifically, non-condensed hydrocarbon group such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned. The (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group. The substituent optionally present in R ¹ to R ³ is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxyl group (—COOH), a nitro group (—NO ₂ ) and the like. Note that the optionally present substituent is not the same as R ¹ to R ³ to be substituted. For example, when R ¹ , R ² and R ³ are alkyl groups, they are not further substituted with an alkyl group. Among these, R ¹ , R ² and R ³ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group. Perhydropolysilazane (PHPS) in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferred. A barrier layer (gas barrier film) formed from such polysilazane exhibits high density.

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and can be a liquid or solid substance (depending on the molecular weight). The perhydropolysilazane may be a commercially available product. Examples of the commercially available product include AQUAMICA NN120, NN120-10, NN120-20, NN110, NAX120, NAX120-20, NAX110, NL120A, NL120-20, NL110A, NL150A, NP110, NP140 (all are made by AZ Electronic Materials Co., Ltd.) and the like.

The content of the polysilazane compound in the nanoparticle-containing polysilazane-containing coating solution varies depending on the desired film thickness of the barrier layer, the pot life of the coating solution, and the like, but is 0. It is preferably 2 to 35% by mass.

Nanoparticle The nanoparticle in the present invention means a particle having an average particle diameter of 1 nm or more and 1000 nm or less as a sphere equivalent diameter.

The nanoparticle of the present invention is at least one kind of metal oxide and metal nitride. The metal of the nanoparticles of the present invention is not particularly limited, but at least selected from the group consisting of Si, Ti, Al, Zr, Zn, Ba, Sr, Ca, Mg, V, Cr, Mo, Li, and Mn. It is preferably selected from oxides and nitrides containing any one element.

The particle size is preferably 1 to 120 nm, more preferably 5 to 100 nm, in terms of a sphere equivalent diameter. If the particle size of the water absorbent is 1 to 120 nm in terms of the equivalent sphere diameter, it is preferable because transparency can be maintained and the amount of water absorption per unit mass is increased. Considering further improvement in gas barrier properties (for example, water vapor barrier properties) and durability, the sphere equivalent diameter of the nanoparticles is more preferably 8 to 90 nm, and particularly preferably 10 to 70 nm.

Here, “sphere equivalent diameter” means the diameter of a sphere when the particle size is converted to a sphere having the same volume as that of the particle. In the present invention, a concentrated particle size analyzer “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd. After measuring dispersibility and measuring dispersibility, an average volume is obtained and converted to a sphere equivalent diameter.

The nanoparticles of the present invention can be appropriately selected from compounds having a water absorption function centering on alkaline earth metals. For example, nano containing at least one selected from the group consisting of Si ₃ N ₄ , TiO ₂ , Al ₂ O ₃ , ZrO ₂ , ZnO, BaO, SrO, CaO, MgO, VO, CrO, MoO ₂ , and LiMnO _2. The particles are included in the nanoparticles used in the present invention. The boehmite type of aluminum oxide is particularly useful. Furthermore, the nanoparticles can be selected from metal elements such as Ti, Mg, Ba, Ca. The nanoparticles can be spherical platelets or other shapes. Platelets or other relatively flat particles (high aspect ratio) may have a partial or complete orientation of the relatively flat surface of a particularly useful particle that may be parallel to the surface of the substrate. Nanoparticles may be included in the coating formulation at 3 to 90 percent, preferably 30 to 75 percent, more preferably 40 to 70 percent of the solid content of the extreme cured coating. The particles may be dispersed in a polar solvent such as DMF, DMSO and water coating formulations. Prior to dispersion of the nanoparticles, their surface may be modified. Silane modified particles, especially epoxy silane modified particles, can be used in embodiments of the present invention. A surfactant may be included for the preparation of a stable dispersion of nanoparticles. Such surfactants include nitric acid, formic acid, citric acid, ammonium citrate, ammonium polymethacrylate, and silane. A polysilazane-containing coating solution may be prepared and the nanoparticles may be added to the curable component that is a dispersion in a solvent.

The nanoparticle content in the nanoparticle-containing polysilazane-containing coating solution varies depending on the desired film thickness of the barrier layer, the pot life of the coating solution, and the like. The content is preferably from 01 to 0.5% by mass.

In addition, the mixing ratio of the polysilazane compound and the nanoparticles is not particularly limited. Considering the effect of improving the adhesion of the barrier layer and gas barrier properties (especially gas barrier properties under high temperature and high humidity), the nanoparticles are preferably 0.5 to 20% by mass with respect to 100% by mass of the polysilazane compound. More preferably, they are mixed at a ratio of 1 to 10% by mass. With such a mixing ratio, the nanoparticles appropriately interact with the Si—N bond of the polysilazane compound, and the strength of the second inorganic layer in a wet heat environment can be further improved. In addition, since the nanoparticles appropriately interact with the first inorganic layer, the adhesion between the first and second inorganic layers can be further improved.

The nanoparticle-containing polysilazane-containing coating solution may further contain an amine catalyst, a metal, and a solvent.

Amine catalyst and metal An amine catalyst and a metal can promote the conversion of a polysilazane compound into a silicon oxide compound in the modification treatment described below.

The amine catalyst that can be used is not particularly limited, but N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N ′ -Tetramethyl-1,3-diaminopropane, N, N, N ', N'-tetramethyl-1,6-diaminohexane.

In addition, the metal that can be used is not particularly limited, and examples thereof include platinum compounds such as platinum acetylacetonate, palladium compounds such as palladium propionate, and rhodium compounds such as rhodium acetylacetonate.

The amine catalyst and the metal are preferably contained in an amount of 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.5 to 2% by mass with respect to the polysilazane compound. When the amount of the catalyst added is within the above range, it is preferable because excessive silanol formation, film density reduction, and film defect increase due to rapid progress of the reaction can be prevented.

Solvent The solvent that can be contained in the nanoparticle-containing polysilazane-containing coating solution is not particularly limited as long as it does not react with the polysilazane compound and the nanoparticles, and a known solvent can be used. Specific examples include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons; ether solvents such as aliphatic ethers and alicyclic ethers. More specifically, examples of the hydrocarbon solvent include pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, methylene chloride, trichloroethane, and the like. Examples of ether solvents include dibutyl ether, dioxane, and tetrahydrofuran. These solvents can be used alone or in admixture of two or more. These solvents can be appropriately selected according to the purpose in consideration of the solubility of the polysilazane compound and the evaporation rate of the solvent.

(Formation of polysilazane coating film)
A polysilazane coating film is formed by applying and drying a polysilazane-containing coating solution containing metal oxide nanoparticles or metal nitride nanoparticles on the first inorganic layer.

As a method of forming a polysilazane coating film by applying a polysilazane-containing coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is preferably 10 to 1000 nm after drying, more preferably 20 to 600 nm, and still more preferably 40 to 400 nm. If the film thickness is 10 nm or more, sufficient barrier properties can be obtained, and if it is 1000 nm or less, stable coating properties can be obtained at the time of layer formation, and high light transmittance can be realized.

After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed.

The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 20 to 200 ° C, more preferably 50 to 120 ° C. When the heat treatment is performed in such a temperature range, it is preferable from the viewpoint of preventing the plastic film from being deformed or its strength from being deteriorated.

(Modification process)
The modification treatment in the present invention refers to a conversion reaction of a polysilazane compound to silicon oxide, and the gas barrier film of the present invention as a whole has a gas barrier property (water vapor permeability is 1 × 10 ⁻³ g / m ² · day). The following is a process for forming an inorganic thin film at a level that can contribute to the development of:

Such a modification treatment can be performed by irradiating vacuum ultraviolet light (hereinafter referred to as “VUV” or “VUV light”) having a wavelength of 200 nm or less.

By using VUV light, the oxidation reaction by active oxygen or ozone is advanced while directly cutting the atomic bonds by the action of only photons called photon processes, so that the silicon oxynitride film or the silicon oxide film is formed at a relatively low temperature. Formation can be performed. In addition, this method is also suitable for manufacturing in a roll-to-roll system with good productivity.

Vacuum ultraviolet light irradiation treatment: excimer irradiation treatment In the present invention, the modification treatment method is treatment by vacuum ultraviolet light irradiation (excimer irradiation treatment). In the treatment by the vacuum ultraviolet light irradiation, the wavelength to be used needs to be 200 nm or less from the viewpoint of efficiently performing the modification, and light energy of 100 to 200 nm larger than the interatomic bonding force in the polysilazane compound may be used. Preferably, light energy having a wavelength of 100 to 180 nm is used, and an atomic bond is directly cut by an action of only a photon called a photon process, so that an oxidation reaction with active oxygen or ozone proceeds and a relatively low temperature (about 200 nm). This is a method of forming a silicon oxide film at a temperature of not higher than ° C.

The light source of vacuum ultraviolet light is not particularly limited, and a known light source can be used. For example, a low pressure mercury lamp, an excimer lamp, etc. are mentioned. Of these, it is preferable to use an excimer lamp, particularly a xenon (Xe) excimer lamp.

Such an excimer light (vacuum ultraviolet light) irradiation apparatus can use a commercially available lamp (for example, Ushio Electric Co., Ltd., M.D.Com Co., Ltd.).

Excimer lamps are characterized in that excimer light is concentrated at one wavelength and almost no light other than the necessary light is emitted, and is highly efficient. Moreover, since excess light is not radiated | emitted, the temperature of a target object can be kept low. Further, since no time is required for starting and restarting, lighting and blinking can be performed instantaneously. In particular, the Xe excimer lamp is excellent in luminous efficiency because it emits short wavelength 172 nm vacuum ultraviolet light at a single wavelength. Since the Xe excimer lamp has a short wavelength of 172 nm and a high energy, it is known that the bond breaking ability of organic compounds is high.

The irradiation intensity of vacuum ultraviolet light irradiation varies depending on the base material used, the composition and concentration of the first barrier layer, etc., but is preferably 1 to 100 kW / cm ² , and preferably 1 to 10 W / cm ^2. Is more preferable.

The time of irradiation with vacuum ultraviolet light varies depending on the substrate used, the composition and concentration of the first barrier layer, etc., but is preferably 0.1 second to 10 minutes, preferably 0.5 seconds to 3 minutes. It is more preferable.

Integrated light quantity of vacuum ultraviolet light is not particularly limited, preferably from 200 ~ 5000mJ / cm ^2, and more preferably 500 ~ 3000mJ / cm ^2. It is preferable that the accumulated amount of vacuum ultraviolet light is 200 mJ / cm ² or more because high barrier properties can be obtained by sufficient modification. On the other hand, when the cumulative amount of vacuum ultraviolet light is 5000 mJ / cm ² or less, it is preferable because a barrier layer having high smoothness can be formed without deformation of the substrate.

Further, the irradiation temperature of the vacuum ultraviolet light varies depending on the substrate to be applied, and can be appropriately determined by those skilled in the art. The irradiation temperature of the vacuum ultraviolet light is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. It is preferable for the irradiation temperature to be within the above-mentioned range since deformation of the base material, deterioration of strength, etc. are unlikely to occur and the characteristics of the base material are not impaired.

Oxygen is required for the reaction at the time of ultraviolet irradiation, but vacuum ultraviolet light is absorbed by oxygen, so the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the concentration and water vapor concentration are low. That is, the oxygen concentration at the time of vacuum ultraviolet light irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), more preferably 50 to 10,000 volume ppm, and most preferably 100 to 5000 ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

As the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet light, a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

Irradiation energy amount of the vacuum ultraviolet light at the coated surface is preferably 200 ~ 10000mJ / cm ^2, and more preferably 500 ~ 5000mJ / cm ^2. If it is 200 mJ / cm ² or more, sufficient modification is possible, and if it is 10,000 mJ / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the substrate can be suppressed.

Further, the vacuum ultraviolet light used for reforming, CO, may be generated by plasma formed in a gas containing at least one of CO ₂ and CH _4.

The coating film to be irradiated with ultraviolet rays is mixed with oxygen and a small amount of moisture at the time of application, and adsorbed oxygen and adsorbed water may also exist in the substrate and adjacent layers. If oxygen or the like is used, the oxygen source required for generation of active oxygen or ozone for performing the reforming process may be sufficient without newly introducing oxygen into the irradiation chamber. Also, since 172 nm vacuum ultraviolet light such as Xe excimer lamp is absorbed by oxygen, the amount of vacuum ultraviolet light reaching the coating film may decrease, so the oxygen concentration should be set low during irradiation with vacuum ultraviolet light. In addition, it is preferable that the vacuum ultraviolet light be able to efficiently reach the coating film.

The film thickness, density, and the like of the barrier layer obtained by the above-described modification treatment can be controlled by appropriately selecting application conditions, vacuum ultraviolet light irradiation conditions, and the like. For example, the film thickness and density of the barrier layer can be controlled by appropriately selecting the irradiation method of vacuum ultraviolet light from continuous irradiation, irradiation divided into a plurality of times, and so-called pulse irradiation, etc. in which the plurality of times of irradiation is short. Can be done.

Further, the film density of the barrier layer can be appropriately set according to the purpose. For example, the film density of the barrier layer is preferably in the range of 1.5 to 2.6 g / cm ³ . Within this range, the density of the film can be improved and deterioration of gas barrier properties and film deterioration under high temperature and high humidity conditions can be prevented.

The second inorganic layer preferably has an appropriate surface smoothness. Specifically, as the smoothness of the surface of the second inorganic layer, the center line average roughness (Ra) of the second inorganic layer is preferably 50 nm or less, and more preferably 10 nm or less. The lower limit of the center line average roughness (Ra) of the second inorganic layer is not particularly limited, but is practically 0.01 nm or more and preferably 0.1 nm or more. If it is the 2nd inorganic layer which has such Ra, the 2nd barrier layer will closely be formed on the 2nd inorganic layer corresponding to the unevenness in the 2nd inorganic layer satisfactorily. For this reason, the second barrier layer more efficiently covers defects such as cracks and dangling bonds generated in the second inorganic layer, thereby forming a dense surface. Therefore, it is possible to more effectively suppress and prevent a decrease in gas barrier properties (for example, low oxygen permeability and high water vapor barrier properties) under high temperature and high humidity conditions. In the present specification, the center line average roughness (Ra) of the barrier layer is a value measured by the method described in the following examples.

The method for forming the second inorganic layer having the centerline average roughness (Ra) is not particularly limited. For example, a method of providing the following control layer between the substrate and the second inorganic layer; a method of providing an intermediate layer (particularly, the following first inorganic layer) between the second inorganic layer and the second barrier layer The method of controlling the surface roughness by selecting the substrate; the method of controlling the surface roughness of the underlayer; the method of performing the surface treatment before applying the PHPS layer; (Ra) can be controlled within the above range.

The degree of the modification treatment is confirmed by determining each atomic composition ratio of silicon (Si) atoms, nitrogen (N) atoms, oxygen (O) atoms, etc. by XPS analysis of the formed second inorganic layer. it can.

Note that the gas barrier film obtained has a high gas barrier property due to the repair effect of the second barrier layer and the like. Therefore, the gas barrier property of the second inorganic layer may be somewhat low. More specifically, the water vapor transmission rate of the second inorganic layer is preferably 0.5 g / m ² · day or less, and more preferably 0.2 g / m ² · day or less. The “water vapor transmission rate” is a value measured by the method described in Examples.

[Functional layer]
Furthermore, the gas barrier film of the present invention may be provided with various functional layers in addition to the inorganic layer of the present invention and the substrate of the present invention. Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and a light extraction efficiency improving layer; a mechanical functional layer such as a hard coat layer and a stress relaxation layer; an antistatic layer and a conductive layer. An electric functional layer such as: an antifogging layer; an antifouling layer; a printing layer, and the like.

Furthermore, the gas barrier having the barrier layer of the present invention in which at least the inorganic layer of the present invention and the organic layer of the present invention are laminated on the surface of the plastic film opposite to the surface on which the barrier layer satisfying the conditions of the present invention is formed. A conductive laminate layer can also be provided. The gas barrier laminate layer prevents stress concentration and breakage on the barrier layer by suppressing the dimensional change of the gas barrier film by preventing the intrusion of water molecules from the opposite side of the film, resulting in increased durability. It has the feature that it can.

The base material of the present invention described above, the first inorganic layer of the present invention, the second inorganic layer of the present invention, the functional layer and other thicknesses are all arbitrarily adjusted by adjusting the coating solution concentration and coating speed. Can do.

[Performance of gas barrier film]
The gas barrier film of the present invention exhibits excellent gas barrier properties. Water vapor permeability of the gas barrier film of the present invention can achieve the following 0.01g ^/ m 2 · day, preferably 0.005g ^/ m 2 · day or less, more preferably 0.003 g / ^{m 2} · day or less, more preferably 0.001 g / m ² · day or less. In the gas barrier film of the present invention, the barrier layer exhibits excellent adhesion. That is, the adhesion between the organic layer of the present invention constituting the barrier layer and the inorganic layer of the present invention is excellent. Such excellent water vapor permeability and adhesion are maintained even after the gas barrier film is bent a plurality of times. Therefore, the barrier film of the present invention is suitably used for a flexible image display element and the like.

[Electronic device]
The gas barrier film of the present invention can be preferably used for a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

(Organic EL device)
Examples of organic EL elements using a gas barrier film are described in detail in JP-A-2007-30387.

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

Example 1-1
[Base material]
A biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) was used as the substrate.

[Production of smooth layer and anchor coat layer]
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the easy-adhesion surface of the substrate, and after applying with a wire bar so that the film thickness after drying becomes 4 μm, drying conditions: 80 ° C. After drying in 3 minutes, using a high-pressure mercury lamp in an air atmosphere, curing conditions: 1.0 J / cm ² curing was performed to form a smooth layer.

The maximum cross-sectional height Rt (p) representing the surface roughness at this time was 16 nm.

The surface roughness is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an AFM (Atomic Force Microscope AFM: manufactured by Digital Instruments), and the minimum tip radius is calculated. Was measured many times in the section having a measurement direction of 30 μm with the stylus of No. 1 and obtained from the average roughness with respect to the amplitude of fine irregularities.

[Production of first inorganic layer (silicon oxycarbide (SiOC))]
A substrate was mounted on the apparatus shown in FIG. 2, and a barrier thin film layer was formed to a thickness of 300 nm on the substrate under the following film forming conditions (plasma CVD conditions). The carbon distribution curve of carbon atoms contained in the obtained first inorganic layer satisfies the above conditions (i) and (ii).

(Film forming conditions)
Feed rate of raw material gas (hexamethyldisiloxane (HMDSO)): 50 sccm (StandardCubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.5 m / min.

[Production of silicon nitride nanoparticles]
As agglomerated fine particles to be pulverized and dispersed, silicon nitride particles (product number 636703 manufactured by Sigma-Aldrich) are mixed to a concentration of 5% by mass using methyl ethyl ketone (MEK) as a dispersion medium, and uniform using a disper. Mixed.

Next, a bead mill ("Super Apex Mill SAM-05 type" manufactured by Kotobuki Giken Kogyo Co., Ltd.) was used as a disperser, and coarse aggregated fine particles were first crushed with a homogenizer to obtain a particle-dispersed stock solution. The particle-dispersed stock solution was put into a 0.5-liter stirring vessel made of zirconia in a bead mill, and stirring particles made of zirconia and having a particle diameter of 20 μm were put so as to be 70% by volume of the stirring vessel.

Fig. 3 shows a pulverization / dispersion device using a circulation system using a bead mill and a dispersion tank. While circulating the particle dispersion stock solution 19 between the bead mill stirring vessel 16 provided with the stirring blade 15 and the dispersion tank 18 provided with the stirring blade 17, the bead mill stirring blade 15 is operated at a rotational speed of 3000 rpm to obtain the particle dispersion stock solution. 19 was stirred. Thereby, the agglomerated fine particles in the particle-dispersed stock solution 19 were pulverized with the agitated particles, and the pulverization / dispersion treatment for dispersing the pulverized fine particles was performed to obtain the average particle size shown in Table 1. The average particle diameter (sphere equivalent diameter) of silicon nitride nanoparticles obtained by pulverization / dispersion in this way is measured using a concentrated particle size analyzer “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd., and the dispersibility is measured. did. The results of average particle diameter (sphere equivalent diameter) are shown in Table 1.

[Preparation of nanoparticle-containing polysilazane-containing coating solution]
Dibutyl ether solution containing 40% by mass of non-catalyzed perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20), and 40% by mass of dihydrolether containing perhydropolysilazane containing amine catalyst (AZ Electronic Materials ( Co., Ltd., NAX120-20), mixed at a ratio of 4: 1, and further coated with a solvent in which the solvent mass ratio of dibutyl ether and 2,2,4-trimethylpentane was 65:35. The dilution was adjusted so that the solid content of the liquid was 5% by mass. To this solution, 5% by mass of a nano silicon nitride particle dispersion having an average particle diameter of 11 nm was added to prepare a coating solution.

The coating solution prepared above was applied to the vapor-deposited film, and a modification (silica conversion) treatment was performed under the following conditions to produce a second inorganic layer with a thickness of 100 nm.

[Formation of barrier layer: Modification (silica conversion) treatment of polysilazane layer by ultraviolet light]
The polysilazane layer thus formed was subjected to silica conversion treatment under the conditions of dew point temperature of −8 ° C. or lower according to the following method.

(UV irradiation device)
Equipment: Ex D irradiation system MODEL manufactured by M.D. Com: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
(Irradiation conditions)
The base material on which the polysilazane layer fixed on the operation stage was formed was subjected to polysilazane modification treatment under the following conditions to form a barrier layer.

Excimer lamp light intensity: 200 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 95 ° C
Oxygen concentration in the irradiation device: 500 ppm
Water vapor concentration in the irradiation device: 50 ppm
Excimer lamp irradiation time: 10 seconds (Example 1-2)
In Example 1-1, a gas barrier film was produced in the same manner as in Example 1-1 except that the average particle diameter of the silicon nitride nanoparticles added to the polysilazane-containing coating solution was 26 nm.

(Example 1-3)
In Example 1-1, a gas barrier film was produced in the same manner as in Example 1-1 except that the average particle diameter of the silicon nitride nanoparticles added to the polysilazane-containing coating solution was 44 nm.

(Example 1-4)
In Example 1-1, a gas barrier film was produced in the same manner as in Example 1-1 except that the average particle diameter of the silicon nitride nanoparticles added to the polysilazane-containing coating solution was 53 nm.

(Example 1-5)
In Example 1-1, a gas barrier film was produced in the same manner as in Example 1-1 except that the average particle diameter of the silicon nitride nanoparticles added to the polysilazane-containing coating solution was 95 nm.

(Example 1-5)
In Example 1-1, a gas barrier film was produced in the same manner as in Example 1-1 except that the average particle diameter of the silicon nitride nanoparticles added to the polysilazane-containing coating solution was 104 nm.

(Example 1-7)
A gas barrier film was produced in the same manner as in Example 1-1, except that titanium oxide nanoparticles having an average particle diameter of 5 nm were added to the polysilazane-containing coating solution.

(Example 1-8)
A gas barrier film was produced in the same manner as in Example 1-7, except that in Example 1-7, the average particle size of the titanium nitride nanoparticles added to the polysilazane-containing coating solution was 50 nm.

(Example 1-9)
A gas barrier film was produced in the same manner as in Example 1-7, except that in Example 1-7, the average particle size of the titanium nitride nanoparticles added to the polysilazane-containing coating solution was 100 nm.

(Example 1-10)
A gas barrier film was produced in the same manner as in Example 1-1, except that alumina nanoparticles having an average particle diameter of 5 nm were added to the polysilazane-containing coating solution.

(Example 1-11)
In Example 1-10, a gas barrier film was produced in the same manner as in Example 1-10 except that the average particle diameter of the alumina nanoparticles added to the polysilazane-containing coating solution was 50 nm.

(Example 1-12)
In Example 1-10, a gas barrier film was produced in the same manner as in Example 1-10, except that the average particle diameter of the alumina nanoparticles added to the polysilazane-containing coating solution was 100 nm.

(Example 1-13)
In Example 1-1, a gas barrier film was prepared in the same manner as in Example 1-1 except that zirconia nanoparticles having an average particle diameter of 5 nm were added to the polysilazane-containing coating solution.

(Example 1-14)
In Example 1-13, a gas barrier film was produced in the same manner as in Example 1-13, except that the average particle diameter of the zirconia nanoparticles added to the polysilazane-containing coating solution was 50 nm.

(Example 1-15)
In Example 1-13, a gas barrier film was produced in the same manner as in Example 1-13, except that the average particle diameter of the zirconia nanoparticles added to the polysilazane-containing coating solution was 100 nm.

(Example 1-16)
A gas barrier film was produced in the same manner as in Example 1-1, except that zinc oxide nanoparticles having an average particle diameter of 5 nm were added to the polysilazane-containing coating solution.

(Example 1-17)
In Example 1-16, a gas barrier film was produced in the same manner as in Example 1-16, except that the average particle diameter of the zinc oxide nanoparticles added to the polysilazane-containing coating solution was 50 nm.

(Example 1-18)
In Example 1-16, a gas barrier film was produced in the same manner as in Example 1-16 except that the average particle diameter of the zinc oxide nanoparticles added to the polysilazane-containing coating solution was 100 nm.

(Comparative Example 1-1)
In Example 1-1, a gas barrier film was prepared in the same manner as in Example 1-1, except that the silicon nitride nanoparticles were not added to the polysilazane-containing coating solution.

Example 2-1
A plastic film was prepared by the following method, and nano-silicon nitride particles having a particle size of 32 nm were used. The thickness of the first inorganic layer (silicon oxycarbide film (SiOC)) was changed to 150 nm. Similarly, a gas barrier film was produced.

A polyethylene naphthalate film (PEN film, 100 μm thick, manufactured by Teijin DuPont, trade name: Teonex Q65FA) was cut into a 20 cm square, and a barrier layer was formed on the smooth surface side in the same manner as in Example 1-1. evaluated.

(Example 2-2)
A gas barrier film was produced in the same manner as in Example 2-1, except that the first inorganic layer (silicon oxide film (SiO ₂ )) was produced by the following method.

On one surface of the plastic film, an SiO ₂ film was formed by plasma CVD under the following film forming conditions.

Film forming condition material gas (hexamethyldisiloxane (HMDSO)) supply amount: 50 sccm
Supply amount of oxygen gas (O ₂ ): 1000 sccm
Degree of vacuum in the vacuum chamber: 3.5Pa
Applied power from the power source for plasma generation: 0.5 kW
Frequency of power source for plasma generation: 13.56 MHz
Film conveyance speed: 0.5 m / min.

(Example 2-3)
A gas barrier film was produced in the same manner as in Example 2-1, except that the first inorganic layer (aluminosilicate film (SiAlO)) was produced by the following method.

The splice roll was loaded into a roll-to-roll sputter coater. The deposition chamber pressure was pumped down to 2 × 10 ⁻⁶ Torr. Using a gas mixture containing 51 sccm argon and 30 sccm oxygen at a pressure of 2 kW and 600 V, 1 millitorr, and a web speed of 0.43 meters / min, a Si—Al (95/5) target (Academic Pris A 150 nm thick SiAlO inorganic oxide layer was deposited on the substrate by reactive sputtering of John Materials (available commercially from Academy Precision Materials).

(Example 2-4)
A gas barrier film was produced in the same manner as in Example 2-2 except that the first inorganic layer (silicon hydronitride film (SiNH)) was produced by the following method.

Film Formation Conditions The first inorganic layer (silicon hydronitride film (SiNH) (N component other than Si: 97) under the same conditions as in Example 2-2 except that the raw material gas of the following plasma CVD raw material gas formulation 1 was introduced. Mol%)).
Plasma CVD source gas recipe 1
Silane gas: 25 sccm
Ammonia gas: 15 sccm
Nitrogen gas: 200sccm
Plasma CVD source gas recipe 2
Silane gas: 25 sccm
Ammonia gas: 50sccm
Nitrogen gas: 165 sccm.

(Example 2-5)
A barrier layer was produced in the same manner as in Example 2-1, except that the first inorganic layer (silicon oxynitride film (SiON)) was produced by the following method.

A silicon oxynitride film (SiON) having a film thickness of 150 nm was formed as a gas barrier film on a base material using a general CVD apparatus (PD-220NA manufactured by Samco Co., Ltd.) that performs film formation by the CCP-CVD method.

As the substrate, a polyethylene naphthalate film (PEN film, 100 μm thickness, manufactured by Teijin DuPont, trade name: Teonex Q65FA) was used. The area of the base material was 300 cm ² .

The substrate was set at a predetermined position in the vacuum chamber, and the vacuum chamber was closed. Next, when the inside of the vacuum chamber was evacuated and the pressure reached 0.01 Pa, silane gas (5% nitrogen dilution) and oxygen gas (5% nitrogen dilution) were introduced as reaction gases. The flow rate of silane gas was 50 sccm, the flow rate of oxygen gas was 5 sccm, and nitrogen gas. Further, the exhaust in the vacuum chamber was adjusted so that the pressure in the vacuum chamber was 100 Pa.

(Comparative Example 2-1)
A barrier film was prepared in the same manner as in Example 2-1, except that a polysilazane modified film (PHPS), which is the second inorganic layer of the present application, was prepared and used as the first inorganic layer in the following manner. Produced.

Formation of polysilazane coating film Polysilazane-containing coating liquid prepared using Si ₃ N ₄ having a particle size of 32 nm without forming a vapor deposition film on the surface of the substrate is dried with a wireless bar. Apply to 300 nm, treat and dry for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH, and further 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) The polysilazane layer was formed by holding and dehumidifying.

(Barrier layer formation: Polysilazane layer modification (silica conversion) treatment with ultraviolet light)
Subsequently, the polysilazane layer formed above was subjected to a modification (silica conversion) treatment under the condition of a dew point temperature of −8 ° C. or lower according to the following method.

Equipment: Ex D irradiation system MODEL manufactured by M.D. Com: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe.

Reforming treatment conditions The base material on which the polysilazane layer fixed on the operation stage was formed was subjected to a reforming treatment under the following conditions to form a barrier layer.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 500 ppm
Excimer lamp irradiation time: 10 seconds.

(Comparative Example 2-2)
A barrier film was produced in the same manner as in Example 2-1, except that the nanoparticles were not added to the polysilazane-containing coating solution.

[Evaluation 1: Evaluation of gas barrier properties]
The gas barrier property of the gas barrier film prepared above was evaluated by measuring the water vapor transmission rate as follows.

(Water vapor permeability measurement sample preparation device)
Vapor deposition device: JEOL Ltd., vacuum evaporation device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular).

(Preparation of water vapor transmission rate measurement sample)
Using a vacuum evaporation system (manufactured by JEOL Ltd., vacuum evaporation system JEE-400), deposit metal calcium with a size of 12 mm x 12 mm on the barrier layer surface of the produced gas barrier film through a mask so that the deposited film thickness becomes 80 nm. Vapor deposited.

Thereafter, the mask was removed in a vacuum state, and aluminum, which is a water vapor-impermeable metal, was vapor-deposited on the entire surface of one side of the sheet and temporarily sealed. Next, the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation). The water vapor transmission rate measurement sample was produced by irradiating ultraviolet rays to cure and adhere the resin and performing main sealing.

The obtained sample (evaluation cell) was stored in a constant temperature and humidity oven Yamato Humidic Chamber IG47M under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method described in JP-A-2005-283561. The amount of moisture permeated into the cell was calculated from the amount of corrosion of metallic calcium.

[Evaluation 2: Long-term storage stability evaluation]
The gas barrier film thus prepared was stored for 30 days under high temperature and high humidity conditions of 85 ° C. and 90% RH, and then the above water vapor barrier property evaluation sample was prepared, and the degree of deterioration resistance (%) was calculated by the following formula. Sex was evaluated.

¡The longer the ranking value, the better the long-term storage.

5: Deterioration resistance is 90% or more.

4: Deterioration resistance is 80% or more and less than 90%.

3: Deterioration resistance is 60% or more and less than 80%.

2: Deterioration resistance is 30% or more and less than 60%.

1: Deterioration resistance is less than 30%.

As shown in Table 1, the gas barrier films according to the present invention having a barrier layer containing nanoparticles (Example 1-1 to Example 1-18) are gas barrier films containing no nanoparticles (Example 1 Compared to 19), the water vapor transmission rate was significantly lower. As described above, the effect that the gas barrier property is greatly improved by using the nanoparticle-containing barrier layer is not limited to the silicon nitride nanoparticles, but also for many metal oxide and metal nitride nanoparticles. It is the same. Further, at least when the average particle diameter of the nanoparticles is about 5 to 100 nm, a sufficient gas barrier property is obtained and the long-term storage property is sufficient.

Furthermore, as shown in Table 2, the gas barrier film according to the present invention having a barrier layer containing nanoparticles exhibited good gas barrier properties and water vapor permeability even when the material of the first inorganic layer was changed. In addition, when the first inorganic layer is formed by vapor deposition (Example 2-1 to Example 2-5), when the first inorganic layer is substituted with a barrier layer obtained by modifying the polysilazane coating film (comparison) Compared to Example 2-1), the gas barrier property was good and the long-term storage property was also excellent. It is considered that the adhesion between the base material and the barrier layer is improved by forming the first inorganic layer by a vapor deposition method.

This application is based on Japanese Patent Application No. 2013-096587 filed on May 1, 2013, the disclosure of which is referred to and incorporated as a whole.

1 ... Gas barrier film,
2 ... base material,
3 ... CVD layer,
101 ... Plasma CVD apparatus,
102 ... Vacuum tank,
103 ... cathode electrode,
105 ... susceptor,
106 ... heat medium circulation system,
107 ... vacuum exhaust system,
108 ... gas introduction system,
109 ... high frequency power supply 160 ... heating and cooling device,
110 ... base material,
31 ... Manufacturing equipment,
32 ... Delivery roller,
33, 34, 35, 36 ... transport rollers,
39, 40 ... film forming roller,
41 ... gas supply pipe,
42 ... Power source for plasma generation,
43, 44 ... Magnetic field generator,
45 ... take-up roller 15 ... stirring blade,
16: Stirring container of bead mill,
17 ... stirring blade,
18: Dispersion tank,
19: Particle dispersion stock solution.

Claims

A first barrier layer (first inorganic layer) formed by vapor deposition on at least one surface of a substrate (support);
A second barrier layer (second inorganic layer) formed by modifying a polysilazane coating film on the first inorganic layer;
A gas barrier film comprising
The polysilazane coating film contains at least one kind of nanoparticles of metal oxide and metal nitride,
The gas barrier film according to claim 1, wherein the modification of the polysilazane coating film is performed by irradiating the polysilazane coating film with vacuum ultraviolet light having a wavelength of 200 nm or less.
The first barrier layer (first inorganic layer) includes silicon oxynitride (SiON), silicon nitride (SiN), hydrogenated silicon nitride (SiNH), silicon oxycarbide (SiOC), silicon oxide (SiO 2 ), aluminum The gas barrier property according to claim 1, which is an oxide, nitride, oxynitride, oxycarbide or oxynitride carbide containing at least one selected from the group consisting of silicate (SiAlO) and silicon oxynitride carbide (SiONC). the film.
An oxide containing at least one element selected from the group consisting of Si, Ti, Al, Zr, Zn, Ba, Sr, Ca, Mg, V, Cr, Mo, Li, and Mn; 3. The gas barrier film according to claim 1, wherein the gas barrier film is at least one selected from the group consisting of nitrides and has an average particle diameter of 5 to 100 nm in terms of a sphere equivalent diameter.
The nanoparticles are at least one selected from the group consisting of Si 3 N 4 , TiO 2 , Al 2 O 3 , ZrO 2 , ZnO, BaO, SrO, CaO, MgO, VO, CrO, MoO 2 , and LiMnO 2. The gas barrier film according to any one of claims 1 to 3, which is a nanoparticle having an average particle diameter of 5 to 100 nm in terms of a sphere equivalent diameter.
Forming a first barrier layer (first inorganic layer) by vapor deposition on at least one surface of a substrate (support);
Applying a polysilazane-containing coating solution containing at least any one kind of metal oxide and metal nitride on the first inorganic layer, and forming a polysilazane coating film by drying;
Modifying the polysilazane coating film by irradiation with vacuum ultraviolet light having a wavelength of 200 nm or less;
The manufacturing method of the gas-barrier film which has this.
An electronic device having the gas barrier film according to any one of claims 1 to 4 or the gas barrier film produced by the method according to claim 5.